Oxyimino-substituted (1R, cis)-cyclopropanecarboxylate pesticides

ABSTRACT

(1R,cis)-cyclopropane compounds, substantially free of other stereoisomers, and having the formula   &lt;IMAGE&gt;   wherein X is chlorine, bromine or OR in which R is hydrogen, a salt-forming cation, an alkyl group or residues of certain other alcohols; and R1 is hydrogen, or certain optionally halogenated hydrocarbyl groups, are highly active pesticides or intermediates therefore.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of Ser. No. 911,743, filedJune 2, 1978 now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention is directed to new oxyimino-substituted compounds, theiruse as pesticides, to pesticidal formulations containing these newcompounds and to certain novel intermediates.

2. Description of the Prior Art

U.S. Pat. No. 3,922,269 describes a class of2,2-dimethyl-3-(oxyiminomethyl)cyclopropanecarboxylic acid esters usefulas insecticides. In the case of such esters of α-substituted asymmetricalcohols, three asymmetric centers and one oxime double bond are presentand therefore a total of sixteen theoretical stereoisomers are possible.Eight theoretical stereoisomers are possible when there is no asymmetriccenter in the alcohol moiety. The above-mentioned patent states thatesters, in which the two hydrogen atoms on the cyclopropane ring are inthe absolute stereochemical relationship equivalent to that in(+)-trans-chrysanthemic acid, tend to be among the most insecticidallyactive of the various isomers and are preferred for that reason. Indeed,only (1R,trans)-cyclopropanecarboxylate oximes were apparently preparedand tested, and form the basis of the working examples.

SUMMARY OF THE INVENTION

It has now been found that certain oxyimino-substitutedcyclopropanecarboxylates derived from the (1R,cis)-form of2,2-dimethyl-3-formyl-cyclopropanecarboxylic acid are useful pesticides(insecticides and acaricides) and exhibit high knockdowncharacteristics.

Therefore, this invention is directed to new (1R,cis)-cyclopropanecompounds, substantially free of other stereoisomers, and having theformula ##STR2## wherein R¹ represents a hydrogen atom, an alkyl groupcontaining from 1 to 10 carbon atoms optionally substituted by one ormore halogen atoms, a (cycloalkyl)alkyl group containing from 3 to 7ring carbon atoms, a total of from 4 to 9 carbon atoms and optionallyring-substituted by one or more halogen atoms, a cycloalkyl groupcontaining from 3 to 7 ring carbon atoms, an alkenyl group containingfrom 3 to 4 carbon atoms optionally substituted by one or more halogenatoms or alkynyl group containing from 3 to 4 carbon atoms or an arylgroup containing from 6 to 12 carbon atoms or an aralkyl groupcontaining from 7 to 10 carbon atoms, each optionally ring-substitutedby one or more halogen atoms; X is chlorine, bromine or OR in which Rrepresents a hydrogen atom, a salt-forming cation, an alkyl groupcontaining from 1 to 20 carbon atoms or a group of the formula ##STR3##D represents H, --CN, --C.tbd.CH or ##STR4## in which R¹³ and R¹⁴ may bethe same or different, each representing a hydrogen atom or an alkylgroup containing from 1 to 10 carbon atoms, Z represents --CH₂ --,--O--, --CO-- or --S--, Z¹ and Z², which may be the same or different,each represent halogen or an alkyl group containing 1 to 4 carbon atomsand n is 0, 1 or 2, with the proviso that when D is --CN, --C.tbd.CH or##STR5## then the alcohol moiety is in the R,S-racemic or in theS-optical configuration.

In the above-formulas, suitable halogen atoms substituents are chlorine,fluorine or bromine.

Since the biological activity of various optical or geometric isomersand diastereoisomer pairs within the (1R,cis)esters of the invention maydiffer somewhat, it may be desirable to use a more active optical and/orgeometric isomer of diastereoisomer pair of the invention substantiallyfree of the other isomers or pair.

The oxime substituent group of the compounds of the invention gives riseto geometric isomerism by virtue of the presence of an asymmetricallysubstituted double bond. These isomers are usually described as follows:##STR6## A useful subclass of the invention comprises (1R,cis) esters inwhich the oxime substituent is in the Z-isomer form as such isomers canbe several times more pesticidally active than when the oximesubstituent is in the E-isomer form or is a mixture of the E- andZ-isomer forms.

It should be noted that compounds wherein R¹ is haloalkyl,(cycloalkyl)alkyl optionally substituted by halogen, haloalkenyl,alkynyl, aryl optionally substituted by halogen, or aralkyl optionallysubstituted by halogen are also novel in the (1R,trans) or racemic formas for example α-cyano-3-phenoxybenzyl(1R,trans)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylate,3-phenoxybenzyl(1R,trans)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylateand α-cyano-3-phenoxybenzyl(1R,trans)-2,2-dimethyl-3-((cyclopentoxyimino)methyl)cyclopropanecarboxylate.These compounds are claimed in applicants' co-pending application U.S.Ser. No. 13,778, now U.S. Pat. No. 4,211,792.

The (1R,cis) esters of the present invention wherein R represents agroup of formula I above are pesticidally active.

The other oxyimino-substituted (1R,cis) cyclopropane compounds describedabove in which X is chlorine, bromine or OR in which R represents ahydrogen atom, a salt-forming cation or an alkyl group are usefulintermediates for the production of the pesticidal esters.

When the (1R,cis) esters of the invention are those where R is offormula I, it is preferred that they be 3-benzylbenzyl esters,3-benzoylbenzyl esters, or 3-phenoxybenzyl esters although each of therings may be substituted by up to 3 chloro and/or methyl groups. Otheresters of particular interest where R is of formula I are those where Zrepresents O or CH₂ and D represents CN or C.tbd.CH, e.g., esters ofα-cyano or α-ethynyl substituted 3-phenoxy-, 3-benzyl or3-benzyloxybenzyl alcohol. Such alcohols are described in U.S. Pat. Nos.3,666,789, 3,835,176 and 3,862,174.

Variations in activity, of course, depend on the individual combinationsof R and R¹ and are somewhat dependent on the susceptibility of anindividual pest to certain structural subtleties in the variouscombinations of R and R¹.

Typical examples of species within the scope of the invention are:

α-ethynyl-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((sec-butoxyimino)methyl)-cyclopropanecarboxylate

α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((propargyloxyimino)methyl)-cyclopropanecarboxylate

3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((isobutoxyimino)methyl)-cyclopropanecarboxylate

α-thiocarbamoyl-3-benzylbenzyl(1R,cis)-2,2-dimethyl-3-(trifluoromethoxyimino)methyl)-cyclopropanecarboxylate

3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((p-chlorophenoxyimino)methyl)cyclopropanecarboxylate

3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((cyclopentoxyimino)methyl)-cyclopropanecarboxylate

3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((2-chloroethoxyimino)methyl)-cyclopropanecarboxylate

α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((1-(cyclopropyl)ethoxyimino)methyl)-cyclopropanecarboxylate

α-ethynyl-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((phenethoxyimino)methyl)-cyclopropanecarboxylate

3-phenylthiobenzyl(1R,cis)-2,2-dimethyl-3-((neopentoxyimino)methyl)-cyclopropanecarboxylate

3-(p-fluorophenoxy)benzyl(1R,cis)-2,2-dimethyl-3-(cyclopropylmethoxyimino)methyl-cyclopropanecarboxylate

Because of their pesticidal utility in agricultural and domesticsituations, preferred compounds of the invention (subject to the sameprovisions stated above) are those wherein R is α-cyano-3-phenoxybenzyl,3-phenoxybenzyl or α-ethynyl-3-phenoxybenzyl and R¹ is an alkyl groupcontaining from 1 to 6 carbon atoms, a (cycloalkyl)alkyl groupcontaining from 3 to 6 ring carbon atoms, a total of from 4 to 8 carbonatoms, and optionally ring-substituted by from 1 to 4 chlorine, fluorineand/or bromine atoms, a cycloalkyl group containing from 3 to 6 ringcarbon atoms, an alkenyl group containing from 3 to 4 carbon atomsoptionally substituted by one or two chlorine fluorine and/or bromineatoms or an alkynyl group containing from 3 to 4 carbon atoms, an arylgroup containing from 6 to 12 carbon atoms or an aralkyl groupcontaining from 7 to 10 carbon atoms.

In the pesticidal (1R,cis) esters of the invention, R¹ preferablyrepresents an alkyl group containing 2 to 6 carbon atoms, such as ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, amyl,isoamyl, tert-amyl, n-hexyl and the like, a (cycloalkyl)alkyl groupcontaining from 3 to 6 ring carbon atoms and a total of from 4 to 8carbon atoms, such as cyclopropylmethyl, 1-(cyclopropyl)ethyl,cyclohexylmethyl and the like, a cycloalkyl group containing 3 to 6 ringcarbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyland the like, an alkenyl or alkynyl group containing 3 to 4 carbon atomssuch as allyl or propargyl and the like, an aryl group containing from 6to 10 carbon atoms such as phenyl or an aralkyl group containing from 7to 10 carbon atoms, such as benzyl, phenethyl or the like.

Preferred because of their pesticidal properties are those (1R,cis)esters wherein R¹ is an alkyl group containing from 2 to 6 carbon atoms,a (cycloalkyl)alkyl or cycloalkyl group containing 4 to 5 carbon atoms,allyl, phenyl or benzyl. Particularly suitable for those compoundswherein R¹ is an alkyl, (cyclopropyl)alkyl or cycloalkyl group containg4 or 5 carbon atoms, particularly n-butyl, isobutyl, tert-butyl,n-pentyl, neopentyl, cyclopentyl, (cyclopropyl)methyl, or(cyclobutyl)methyl.

Because of their pesticidal activity and ease of preparation, onepreferred subclass of the invention are those esters wherein R isderived from 3-phenoxybenzyl alcohol. Examples of some highly activecompounds of this subclass of the invention are:

3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylateand

3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-(isobutoxyimino)methyl)cyclopropanecarboxylate.

Because of their pesticidal activity, another preferred subclass of theinvention are those (1R,cis) esters derived from α-cyano-3-phenoxybenzylalcohol, particularly in the S-optical configuration. In fact, the(1R,cis) esters wherein the alcohol substituent is in theR-α-cyano-3-phenoxybenzyl alcohol form are without practicalinsecticidal utility. Thus, one preferred embodiment of the invention isdirected to those (1R,cis) esters derived from α-cyano-3-phenoxybenzylalcohol in which such alcohol is in a racemic or, alternatively, in aS-optical configuration. Examples of some highly active compounds ofthis subclass of the invention are the following compounds wherein R isderived from α-cyano-3-phenoxybenzyl alcohol and R¹ is an alkyl,(cycloalkyl)alkyl or cycloalkyl group containing 4 to 5 carbon atoms:

α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylate,

α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((n-butoxyimino)methyl)cyclopropanecarboxylate,

α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((isobutoxyimino)methyl)cyclopropanecarboxylate,

α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((tertbutoxyimino)methyl)cyclopropanecarboxylate,

α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((neo-pentoxyimino)methyl)cyclopropanecarboxylate,and

α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((cyclopentoxyimino)methyl)cyclopropanecarboxylate

which compounds are pesticidally active when the alcohol moiety ispresent in the R,S-racemic or S-optically active form, and the oximesubstituent is in the Z-isomer form or in a mixture of the E- andZ-isomer forms.

A particularly preferred subclass of the invention are those (1R,cis)esters derived from the S-α-cyano-3-phenoxybenzyl alcohol and whereinthe oxime substituent is the Z-isomer form.

It has been observed that esters, wherein the oxime substituent is inthe Z-isomer form, are the most pesticidally active. Therefore, theZ-isomers (or mixtures of isomers in which the Z-isomer predominates)form another preferred subclass of the (1R,cis) esters of the invention.That the Z-isomer form is more pesticidally active contrasts withanother class of oxime pesticides disclosed in U.S. Pat. No. 4,079,149,in which the E-isomer form is said to be the more pesticidally active ofthe oxime geometric isomer forms.

Because of their useful pesticidal properties, one preferred class of(1R,cis) esters of the invention comprise those compounds wherein R¹ is(cycloalkyl)alkyl and R is one of the groups of formula I. Particularlypreferred are (1R,cis) esters wherein R¹ is cyclobutylmethyl orcyclopropylmethyl, and R is 3-phenoxybenzyl or α-cyano-3-phenoxybenzylor individual diastereoisomers of such (1R,cis) esters.

When R is a salt-forming cation, it is selected from alkali metals,alkaline earth metals, aluminum, heavy metals, such as copper, silver,nickel and the like, ammonia or a tetrahydrocarbylammonium compound inwhich the total number of carbon atoms in the hydrocarbyl groups isbetween 4 and 70 carbon atoms. The hydrocarbyl groups can be alkyl,aryl, aralkyl and the like. Preferably, the hydrocarbyl groups areselected from alkyl groups containing from 1 to 10 carbon atoms andaralkyl groups containing from 7 to 10 carbon atoms.

When R is an alkyl group, it contains from 1 to 20 carbon atoms, andpreferably from 1 to 6 carbon atoms, for example, methyl, ethyl,n-propyl, tert-butyl and the like.

The pesticidal (1R,cis) esters of the present invention may be preparedby esterification involving the reaction of an alcohol or derivativethereof of formula RQ e.g., of formula II, and a (1R,cis)-cyclopropanecarboxylic acid or derivative thereof formula III, ##STR7## where Q andCOP are functional groups or atoms which will react to form an esterlinkage and Z¹, Z² and n are as defined above.

It is usually convenient in practice either to treat the acid or acidhalide with the alcohol (COP═COOH or CO--halide and Q═OH) or to treat ahalogeno compound (Q═halogen) with a salt of the carboxylic acid(COP═COO-- M where M is, for example, a silver or triethylammoniumcation).

Transesterification is not always practical and, it is useful to preparethe intermediate (1R,cis) alkyl ester as a tert-butyl ester(R=tert-butyl) which can be selectively converted (under acidconditions) to give the free acid which can, after conversion to theacid halide, be esterified to a pesticidal (1R,cis) ester.

Suitable routes to the (1R,cis) esters in which D is ##STR8## aresimilar to those described in Belgian Pat. No. 839,360. One routeinvolves treating the corresponding nitrile (D is --CN) with hydrogensulfide in the presence of a basic catalyst, preferably in the presenceof a solvent. Useful solvents are lower alkanols, pyridine, orpreferably a dipolar aprotic solvent, such as dimethylformamide orhexamethylphosphoramide. The catalyst is preferably a strongnitrogeneous base, particularly a tertiary amine such as triethylamine,trimethylamine, or the like, or an alkanolamine, such as triethanolamineand the like. The reaction can be carried out at room temperature. It isdesirable that the reaction solution be saturated with hydrogen sulfide.

The (1R,cis) alkyl esters of the present invention can also be preparedby treating an ester of (1R,cis)-caronaldehyde of formula IV ##STR9##where R is an alkyl group, with hydroxylamine or an O-substitutedhydroxylamine of formula R¹ ONH₂ where R¹ is as defined above, and inthe case where R¹ represents hydrogen, subsequently hydrocarbylating theresulting oxime, if desired, with an alkyl (or alkenyl) halide or thelike, to give an alkoxime (or alkenyloxime), etc. Oxime formation cantake place by treating substantially equimolar amounts of aldehyde andhydroxylamine or hydrocarbyloxyamine in a polar solvent such as analkanol, e.g., ethanol or dioxane. When the aldehyde is converted intothe oxime by reaction with hydroxylamine and it is desired to convertthe resulting oxime into an alkylated or alkenylated derivative or thelike, this reaction may be carried out by procedures customarily usedfor the alkylation of phenols. Thus, the oxime may be treated in a polarsolvent, such as ethanol, with an alkyl halide, typically the bromide,in the presence of a hydrogen halide acceptor and the mixture heateduntil reaction is complete.

Oxime formation is normally carried out using an acid addition salt ofhydroxylamine or the hydrocarbyloxyamine, e.g., the hydrochloride. It isconvenient to form the oxime first and subsequently to hydrocarbylatethe oxime. Certain analogs can not be prepared by alkylation of the═NOH) e.g., neopentyl and t-butyl.

Alcohols of formula RQ where R is a group of formula I may be preparedby reduction of the corresponding acids or esters or aldehyde e.g., withhydride, or by conversion of the corresponding halide to an ester, e.g.,by reaction with sodium acetate, followed by hydrolysis of the ester orby reaction of formaldehyde with a Grignard reagent derived from anappropriate halide. The halides of formula RQ where R is a group offormula I minus D can be prepared by halomethylation of the compound##STR10## or side chain halogenation of ##STR11##

Alternatively, in another modification, the compounds of the inventionare prepared by treating (1R,cis)-caronaldehydic acid previouslydescribed in U.S. Pat. No. 3,723,469 and having the formula ##STR12##with an O-substituted hydroxylamine salt of the formula R¹ ONH₃ --Wwherein R¹ is as defined above and W is the anion of salt-forminginorganic acid. Suitable inorganic acids include hydrohalogenic acidssuch as hydrochloric and hydrobromic, sulfur acids such as sulfuric, andphosphorous acids such as phosphoric. Organic acids, such as oxalic acidand the like, are also suitable to form salts.

The reaction is preferably conducted in an aqueous medium in thepresence of a buffer, such as an alkali metal salt of a polybasic acid,including sodium hydrogen carbonate, potassium hydrogen tartrate,disodium hydrogen phosphate and the like. Generally, at least one moleof buffer is used for each mole of (1R,cis)-caronaldehydic acid.

The molar ratio of reactants is not critical and can be widely varied,generally a molar ratio of the O-substituted hydroxylamine salt to(1R,cis)-caronaldehydic acid is suitably from about 1.0 to about 1.5 andpreferably from about 1.02 to about 1.3.

The reaction is generally conducted in the liquid phase by agitating,e.g., stirring, a mixture of the reactants. The resulting product isrecovered by conventional techniques such as filtering, extracting orthe like.

The reaction temperature is not critical and can easily range fromambient to the reflux temperature of any solvent employed at normalpressure. Generally, the temperature is between about 0° C. to about 50°C.

A minor amount of co-solvent can be used in the reaction medium.Suitable co-solvents are lower alcohols containing from 1 to 6 carbonatoms, such as methanol, ethanol and the like.

The resulting (1R,cis)-acids are converted to the ester compounds of theinvention, for example, by reaction with the arylmethyl halide, in thepresence of triethylamine, in a solvent, such as refluxing ethylacetate.

As isomer mixture of the (1R,cis) esters of the invention are readilyseparated into the individual diastereoisomers using known procedures,as for example, by preparative scale liquid chromatography. One suchchromatographic system which can be employed has the followingcharacteristics:

Column--porisil polar bonded phase, 9.2×250 mm

Mobile Phase--8% v/v diethyl ether in n-hexane

Flow Rate--2.5 ml/min

Detection--UV₂₅₄ at 2.0 AUFS

Injection--typically 500 ml of a 20 mg/ml solution in the mobile phase.

Such a procedure readily yields the single diastereoisomers in greaterthan 90% purity (as determined by NMR analysis). In the case of (1R,cis)esters of α-substituted alcohols four diastereoisomers are obtained.

Since it has been discovered that the (1R,cis) esters of the inventionin which the oxime substituent is in the Z-isomer form are pesticidallymore active than when the oxime substituent is in either the E-isomerform or is a mixture of E- and Z-isomer forms, it can be desirable toconvert the esters in E-isomer form into a mixture of esters in both theE- and Z-isomer forms. Such conversion is accomplished by the additionof a minor amount of an organic or inorganic acidic material. Anyinorganic or organic acid or acidic acting material can be used,including acidic clays such as acidic silicates and aluminates orsynthetic acidified clays, mineral acids such as hydrochloric orsulfuric acid, sulfonic acids such as toluenesulfonic acid, or organicacids, including lower alkanoic acids such as acetic, propionic orbutyric acids. The acid can be used in a solid or liquid form. While theprecise amount of acid used to convert the E-isomer or Z-isomer into theE- and Z-isomer mixture can vary depending on the particularoxyimino-substituted (1R,cis) ester, from 0.001 to 5% by weight of acidbased on the E-isomer or Z-isomer is generally sufficient. Preferably,from 0.01 to 5% by weight of acid is used.

The invention includes, within its scope, pesticidal compositionscomprising a pesticidally acceptable adjuvant--that is, at least onecarrier or a surface-active agent--and, as active ingredient, at leastone pesticidally active (1R,cis) ester of this invention. Likewise, theinvention includes also a method of combatting insect, acarine or otheranthropod pests at a locus which comprises applying to the pests or tothe locus a pesticidally effective amount of at least one compound ofthe invention.

With respect to the spectrum of pesticidal activity, the compounds ofthis invention exhibit a selective or non-selective activity on suchorders as Coleoptera, Lepidoptera (especially larvae), Diptera,Orthoptera, Hemiptera, Homoptera and Acarina depending upon a specificcombination of acid and an alcohol according to the present invention.The compositions according to the present invention are very useful forcontrolling disease carrying insects such as mosquitoes, flies andcockroaches, grain insects such as rice weevil (Sitophilus oryzae) andmites as well as agricultural noxious insects such as planthoppers,green rice leafhopper (Nephotettix bipuntatus cinticeps Uhler),diamond-back moths (Plutella maculipennis Curtis), imported cabbage worm(Pieris rapae Linne), rice stem borers (Chilo suppressalis Walker), cornearworm larvae (Heliothis zea Boddie), aphids, tortrixes, leaf-minersand the like.

The (1R,cis) esters are used for harvested crops, horticulturalapplication, forests, cultures in green house, and packaging materialsfor foodstuffs, household applications and as ectoparasiticides.

The term "carrier" as used herein means a material, that may beinorganic or organic and of synthetic or natural origin with which theactive compound is mixed or formulated to facilitate its application tothe plant, seed, soil and other object to be treated, or its storage,transport or handling. The carrier may be a solid or a liquid.

Suitable solid carriers may be natural and synthetic clays andsilicates, for example, natural silicas such as diatomaceous earths;magnesium silicates, for example, talcs; magnesium aluminum silicates,for example, attapulgites and vermiculites; aluminum silicates, forexample, kaolinites, montmorillonites and micas; calcium carbonate;calcium sulfate; synthetic hydrated silicon oxides and synthetic calciumor aluminum silicates; elements such as for example, carbon and sulfur;natural and synthetic resins such as, for example, coumarone resins,polyvinyl chloride and styrene polymers and copolymers; solidpolychlorophenols; bitumen, waxes such as beeswax, paraffin wax, andchlorinated mineral waxes; degradable organic solids, such as groundcorn cobs and walnut shells; and solid fertilizers, for examplesuperphosphates.

Suitable liquid carriers include solvents for the compounds of thisinvention and liquids in which the toxicant is insoluble or onlyslightly soluble.

Examples of such solvents and liquid carriers, generally, are water,alcohols, for example, isopropyl alcohol, ketones, such as acetone,methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers;aromatic hydrocarbons such as benzene, toluene and xylene; petroleumfractions, such as kerosene, light mineral oils, chlorinatedhydrocarbons, such as methylene chloride, perchlorethylene,trichloroethane, including liquified normally vaporous gaseouscompounds. Mixtures of different liquids are often suitable.

If used, the surface-active agent may be an emulsifying agent or adispersing agent or a wetting agent. It may be nonionic, ionic orpreferably, mixtures of both. Surface-active agents usually applied informulating pesticides may be used. Examples of such surface-activeagents are the sodium or calcium salts of polyacrylic acids and ligninsulfonic acids; the condensation products of fatty acids or aliphaticamines or amides containing at least 12 carbon atoms in the moleculewith ethylene oxide and/or propylene oxide; fatty acid esters ofglycerol, sorbitan, sucrose or pentaerythritol; fatty acids salts of lowmolecular weight, mono-, di- and trialkyl-amines; condensates of thesewith ethylene oxide and/or proplyene oxide; condensation products offatty alcohols or alkyl phenols, for example, p-octylphenol orp-octylcresol, with ethylene oxide and/or propylene oxide; sulfates orsulfonates of these condensation products; alkali or alkaline earthmetal salts, preferably sodium salts of sulfonated castor oil, andsodium alkylaryl sulfonates such as sodium dodecylbenzene sulfonate; andpolymers of ethylene oxide and copolymers of ethylene oxide andpropylene oxide.

The compositions of the invention may be formulated as wettable powders,dusts, granules, solutions, emulsifiable concentrates, emulsions,suspension concentrates or aerosols. Encapsulated formulations andcontrolled release formulations are also contemplated, as are baitformulations. Wettable powders are usually compounded to contain 25, 50or 75% w of toxicant and usually contain, in addition to solid carrier,3-10% w of stabilizer(s) and/or other additives such as penetrants orstickers. Dusts are usually formulated as a dust concentrate having asimilar composition to that of a wettable powder but without adispersant, and are diluted in the field with further solid carrier togive a composition usually containing 178-10% w of toxicant. Granulesmay be manufactured by extrusion of plastics, agglomeration orimpregnation techniques. Generally, granules will contain 178-25% wtoxicant and 0-10% w of additives such as stabilizers, slow releasemodifiers and binding agents. Emulsifiable concentrates usually contain,in addition to the solvent, and when necessary, cosolvent, 10-50% w/vtoxicant, 2-20% w/v emulsifiers and 0-20% w/v of appropriate additivessuch as stabilizers, penetrants and corrosion inhibitors. Suspensionconcentrates are compounded so as to obtain a stable, nonsedimenting,flowable product and usually contain 10-75% w toxicant, 0-5% w ofdispersing agents, 0.1-10% w of suspending agents such as protectivecolloids and thixotropic agents, 0-10% w of appropriate additives suchad defoamers, corrosion inhibitors, stabilizers, penetrants andstickers, and as carrier, water or an organic liquid in which thetoxicant is substantially insoluble; certain organic additives orinorganic salts may be dissolved in the carrier to assist in preventingsedimentation or as antifreeze agents for water.

Aqueous dispersions and emulsions, for example, compositions obtained bydiluting a wettable powder or an emulsifiable concentrate according tothe invention with water, also lie within the scope of the presentinvention.

The compositions of the invention can also contain other ingredients,for example, other compounds possessing pesticidal, herbicidal orfungicidal properties, or attractants, such as pheromones, attractivefood ingredients, and the like, for use in baits and trap formulations.

Particularly useful compositions can be obtained by using a mixture oftwo or more kinds of the present compounds, or by the use of synergists,such as those known for use with the general class of "pyrethroid"compounds, especiallyα-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene alsoknown as piperonyl butoxide,1,2-methylenedioxy-4-[2-(octylsulfinyl)propyl]benzene,4-(3,4-methylenedioxyphenyl)5-methyl-1,3-dioxane also known assafroxane, N-(2-ethyhexyl)bicyclo[2,2,1]hept-5-ene-2,3-dicarboximide,octachlorodipropyl ether, isobornyl thiocyanoacetate, and othersynergists used for allethrin and pyrethrin. Useful compositions can beprepared with other biological chemicals including othercyclopropanecarboxylates, organic phosphate type insecticides andcarbamate type insecticides.

The compositions of the invention are applied in sufficient amount tosupply the effective dosage of toxicant at the locus to be protected.This dosage is dependent upon many factors, including the carrieremployed, the method and conditions of application, whether theformulation is present at the locus in the form of an aerosol, or as afilm, or as discrete particles, the thickness of film or size ofparticles, the insect or acarine species to be controlled and the like,proper consideration and resolution of these factors to provide thenecessary dosage of active material at the locus being within the skillof those versed in the art. In general, however, the effective dosage oftoxicants of this invention at the locus to be protected--i.e. theapplied dosage--is of the order or 0.01% to 0.5% based on the totalweight of the formulation, though under some circumstances the effectiveconcentration will be as little as 0.001% or as much as 2%, on the samebasis.

The superior activity of the (1R,cis) esters of the invention isusefully employed when such an ester is present in an amountsubstantially greater than that usually present in the racemate of anoxyimino substituted ester. Therefore, use of the (1R,cis) esters of theinvention in a form substantially free of other stereoisomers ispreferred, for example in a (1R,cis) isomer purity of greater than about85%, preferably in a (1R,cis) isomer purity greater than about 90% oreven greater than 95%.

ILLUSTRATIVE EMBODIMENTS

The invention is illustrated by the following embodiments which describethe preparation and biological testing of typical species of theinvention with respect to representative insects and acarines. Theembodiments are presented for the purpose of illustration only andshould not be regarded as limiting the invention in any way. Theidentity of the products, including intermediates, was confirmed byelemental, infrared and nuclear magnetic resonance spectral (NMR)analyses as necessary.

EMBODIMENT 1(1R,cis)-2,2-dimethyl-3-((isobutoxyimino)methyl)cyclopropanecarboxylicacid

A solution of 1.7 g of (1R,cis)-caronaldehydic acid and 1.6 g ofisobutoxyamine hydrochloride in 50 ml of water was stirred at roomtemperature for 5 hours in the presence of 2.2 g of sodium bicarbonate.The resulting mixture was filtered through celite, the filtrate wasacidified with concentrated hydrochloric acid, the resulting solutionwas extracted with methylene chloride, and the combined extracts weredried over magnesium sulfate and stripped to give 2.4 g of desiredproduct as an oil; [α]_(D) ²⁵ +33.2° (CHCl₃ ; c=0.02 g/cc).

EMBODIMENT 2 α-Cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-(isobutoxyimino)methyl)cyclopropanecarboxylate

A solution of 2.1 g of(1R,cis)-2,2-dimethyl-3-(isobutoxyimino)methyl)cyclopropanecarboxylicacid, 2.9 g of α-cyano-3-phenoxybenzyl bromide, 1 g of triethylamine and25 ml of ethyl acetate was refluxed for about three hours and allowed tostand at room temperature for two days. The reaction mixture was dilutedwith methylene chloride and washed with water. The methylene chloridephase was then dried over magnesium sulfate and stripped to give 5 g ofamber oil. This oil was chromatographed on a 3 foot silica gel columnwith a mixture of etherpentane (1:15 ratio) as the eluant to give ayellow oil. Rechromatographing this product with a 1:9 ratio ofether-pentane as the eluant gave 3.4 g of product as a yellow oil;[α]_(D) ²⁵ +12.1° (CHCl₃ ; c=0.02 g/cc).

EMBODIMENT 3 α-Cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((neopentoxyimino)methyl)cyclopropanecarboxylate

A solution of 1.4 g of(1R,cis)-2,2-dimethyl-3-((neopentoxyimino)methyl)cyclopropanecarboxylicacid in 10 ml of toluene was added to a mixture of 0.05 g oftetrabutylammonium hydrogen sulfate, 0.05 g benzyltriethylammoniumchloride, 0.42 g potassium carbonate in 6 ml water. 1.6 g ofα-cyano-3-phenoxybenzyl bromide was added and the resulting mixture wasvigorously stirred for 6 hours at 70°-75° C., then allowed to separateinto layers. The toluene layer was washed with water, then withsaturated sodium bicarbonate solution and finally with saturated sodiumchloride solution. The resulting solution was dried over magnesiumsulfate and stripped to give an oil. This oil was chromatographed onsilica gel with a mixture of ether-pentane (4:1 ratio) as the eluent togive 2.2 g of a thick yellow oil [α]_(D) ²⁵ +7.5° (CHCl₃ ; c=0.02 g/cc).The(1R,cis)-2,2-dimethyl-3-((neopentoxyimino)methyl)cyclopropanecarboxylicacid was prepared by a method similar to that used in Example 1 suchthat neopentoxyamine hydrochloride was reacted with(1R,cis)caronaldehydic acid.

EMBODIMENT 4 (3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((allyloxyimino)methyl)cyclopropanecarboxylate

A solution of 3.7 g of 3-phenoxybenzyl bromide and 2.8 g of(1R,cis)-2,2-dimethyl-3-((allyloxyimino)methyl)cyclopropanecarboxylicacid (prepared by a method similar to that shown in Embodiment I) and1.4 g of triethylamine in 30 ml of ethyl acetate was refluxed for 21/2hours. The reaction mixture was diluted with ether and washed withwater. The ether phase was dried over magnesium sulfate, filtered andstripped to give an oil. This oil in methylene chloride was passedthrough a florisil column to give 2.5 g of the desired product as an oil[α]_(D) ²⁵ +22.9° (CHCl; c=0.012 g/cc).

EMBODIMENTS 5-20

Procedures similar to those of Embodiments 2-4 were used to prepareadditional compounds of the invention shown in Table 1 below:

                                      TABLE 1                                     __________________________________________________________________________    Oxyimino-substituted (1R,cis)-Cyclopropanecarboxylates                         ##STR13##                                                                    __________________________________________________________________________    Embodiment                                                                           R.sup.1      R            Isomer Z/E                                                                           [α].sub.D.sup.25                                                        (CHCl.sub.3)                          __________________________________________________________________________     5     CH.sub.3     α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                           +17.9°                          6     CH(CH.sub.3).sub.2                                                                         α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                           +19.6°                          7     CH.sub.2 CHCH.sub.2                                                                        α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                           +22.1°                          8     benzyl       α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                           +30.0°                          9     C.sub.2 H.sub.5                                                                            α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                           not det.                              10     CH(CH.sub.3)C.sub.2 H.sub.5                                                                α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                           +23.8°                         11     phenyl       α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                           not det.                              12     CH.sub.3     3-phenoxybenzyl                                                                            E-Z-isomer                                                                           +10.0°                         13     n-C.sub.3 H.sub.7                                                                          α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                           +16.7°                         14     n-C.sub.4 H.sub.9                                                                          α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                           +20.0°                         15     C(CH.sub.3).sub.3                                                                          α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                           +17.5°                         16     CH.sub.2 (CH.sub.2).sub.4 CH.sub.3                                                         α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                           not det.                              __________________________________________________________________________    Embodiment                                                                           R.sup.1      R            E/Z Isomer                                                                           [α].sub.D.sup.25                                                        (CHCl.sub.3)                          __________________________________________________________________________    17     CH.sub.2 (CH.sub.2).sub.4 CH.sub.3                                                         α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                            +5.0°                          18a   CH.sub.2 CH(CH.sub.3).sub.2                                                                3-phenoxybenzyl                                                                            E-Z-isomer                                                                            +5.0°                          18b   CH.sub.2 CH(CH.sub.3).sub.2                                                                3-phenoxybenzyl                                                                            E-isomer                                                                             +21.2°                          18c   CH.sub.2 CH(CH.sub.3).sub.2                                                                3-phenoxybenzyl                                                                            Z-isomer                                                                             +23.8°                         19     CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                       α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                           +10.0°                         20     CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                                                     α-cyano-3-phenoxybenzyl                                                              E-Z-isomer                                                                            +6.2°                         __________________________________________________________________________

EMBODIMENT 21(1R,cis)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylicacid

A solution of 1.7 g of (1R,cis)-caronaldehydic acid and 1.6 g ofcyclopropylmethoxyamine hydrochloride in 50 ml of water was stirred atroom temperature for about 4 hours in the presence of 2.2 g of sodiumbicarbonate. The resulting mixture was filtered through celite and thefiltrate was acidified to pH 4 with concentrated hydrochloric acid. Theresulting solution was extracted with methylene chloride and thecombined extracts were dried over magnesium sulfate and stripped to give2.0 g of the desired product as an oil; [α]_(D) ²⁵ +30.0° (CHCl₃ ;c=0.02 g/cc).

EMBODIMENT 22 α-cyano-3-phenoxybenzyl(1R,cis)-3-(cyclopropylmethoxyimino)methyl)cyclopropanecarboxylate

A solution of 1.9 g of(1R,cis)-2,2-dimethyl-3-(cyclopropylmethoxyimino)methyl)cyclopropanecarboxylicacid, 2.6 g of α-cyano-3-phenoxybenzyl bromide, 0.9 g of triethylamineand 25 ml of ethyl acetate was heated on a steam bath for three hoursand allowed to stand at room temperature for two days. The reactionmixture was diluted with diethyl ether and washed with water. The etherphase was dried over magnesium sulfate and stripped to give 3.8 g of anamber oil. This oil was chromatographed on a three foot silica gelcolumn with a mixture of pentane-ether (9:1 ratio) as eluant to give 2.6g of desired product as a yellow oil; [α]_(D) ²⁵ +11.2° (CHCl₃ ; c=0.02g/cc).

EMBODIMENT 23 3-Phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylate

Following a procedure similar to that of Embodiments 4 and 22 above, 2.3g of 3-phenoxybenzyl bromide was treated with 1.8 g of(1R,cis)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylicacid to yield (a) 1.9 g of the desired carboxylate product, as acolorless oil, as a mixture of E- and Z-isomers; [α]_(D) ²⁵ +12.5°(CHCl₃ ; c=0.02 g/cc).

1.5 g of this product was rechromatographed by the same procedure toyield two products determined by NMR as (b) 0.5 g of the E-isomer as theproduct having the higher R_(f) value, and (c) 0.6 g of the Z-isomer asthe product having the lower R_(f) value.

EMBODIMENT 24 α-Cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((2,2-dichlorocyclopropylmethoxyimino)methyl)cyclopropanecarboxylate.

Following a procedure similar to that of Embodiment 22 above, 1.4 g ofα-cyano-3-phenoxybenzyl bromide was treated with(1R,cis)-2,2-dimethyl-3-((2,2-dichlorocyclopropylmethoxyimino)methyl)cyclopropanecarboxylicacid (prepared from (1R,cis)-caronaldehydic acid and2,2-dichlorocyclopropylmethoxyamine hydrochloride as in Embodiment 21)to yield 2.2 g of the desired carboxylate product as a pale yellow oil;[α]_(D) ²⁵ +12.5° (CHCl₃ ; c=0.2 g/cc).

EMBODIMENT 25 Diastereoisomers of α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((isopropoxyimino)methyl)cyclopropanecarboxylate

An isomer mixture of R,S-α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((isopropoxyimino)methyl)cyclopropanecarboxylate(E-Z mixture), prepared as in Embodiment 6 above, was separated into itsfour (4) diastereoisomeric forms using a preparative scale liquidchromatograph (LC). The chromatographic system employed was:

Column--porisil polar bonded phase 9.2×250 mm.

Mobile Phase--8% v/v diethyl ether in n-hexane.

Flow Rate--2.5 ml/min.

Detection--UV₂₅₄ at AUFS.

Injection--typically 500 ml of a 20 mg/ml solution in the mobile phase.

The individual diastereoisomers were isolated in greater than 90% purity(as determined by NMR analysis) and are set forth in Table 2 below interms of their stereoisomeric configuration and column retention time.

                  TABLE 2                                                         ______________________________________                                        Diastereoisomers of α-cyano-3-phenoxybenzyl (1R,cis)-2,2-               dimethyl-3-((isopropoxyimino)methyl)cyclopropanecarboxylate.                          Configuration                                                         Embodiment                                                                              Oxime    Alcohol   Retention Time (min)                             ______________________________________                                        25 a      E        R         6.6                                              25 b      E        S         7.8                                              25 c      Z        R         7.2                                              25 d      Z        S         8.4                                              ______________________________________                                    

Following procedures similar to Embodiment 25 above:α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((n-butoxyimino)methyl)cyclopropanecarboxylate,α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((n-pentoxyimino)methyl)cyclopropanecarboxylate,α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((cyclopentoxyimino)methyl)cyclopropanecarboxylate,α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((n-propoxyimino)methyl)cyclopropanecarboxylate,and α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((isoamyloxyimino)methyl)cyclopropanecarboxylateare separated into their individual diastereoisomers.

EMBODIMENT 26-59

Using procedures similar to those of Embodiments 1-25 above, thefollowing cyclopropane derivatives were prepared as set out in Table 3.

EMBODIMENT 60 Pesticidal Activity

Activity of the compounds of this invention with respect to insect andacarine pests was determined by using standardized test methods to testthe toxicity of the compounds as follows:

I. Houseflies (Musca domestica (Linne)) were tested by placing 50 4- to5-day old houseflies into a spray cage and spraying with 0.6 ml of asolution of test compound. After spraying, the flies were anesthetizedwith CO₂ and transferred to a recovery cage containing a milk pad forfood. The cages were held for 18-20 hours after which mortality countswere made. Both dead and moribund were counted. The tests were conductedemploying several different dosage rates of each test compound.

II. Pea aphids (Acrythosiphon pisum (Harris)) were tested by placingabout 100 aphids on broad bean plants. The plants were sprayed withdilutions of acetone solution of test compound into water containing anemulsifier and held in containers under laboratory conditions for 18 to20 hours at which time the living aphids in the containers were counted.The tests were conducted employing several different dosage rates ofeach test compound.

                                      TABLE 3                                     __________________________________________________________________________    Oxyimino-substituted (1R,cis)-Cyclopropane Derivatives                         ##STR14##                                                                                                     [α].sub.D.sup.25 (CHCl.sub.3)          Embodiment                                                                           R.sup.1      R            c = 0.02 g/cc                                __________________________________________________________________________    26                                                                                    ##STR15##   α-cyano-3-phenoxybenzyl                                                              +10.0°                                27                                                                                    ##STR16##   α-cyano-3-phenoxybenzyl                             28                                                                                    ##STR17##   α-cyano-3-phenoxybenzyl                                                               +7.5                                        29     CH.sub.2 C(CH.sub.3)CH.sub.2                                                               α-cyano-3-phenoxybenzyl                                                               +8.8                                        30     CHCH(CH.sub.3)CH.sub.2 CH.sub.3                                                            α-cyano-3-phenoxybenzyl                                                              +12.5                                        (single isomer configuration in R.sup.1)                                      31     CH.sub.2 CH.sub.2 CHCHCH.sub.3                                                             α-cyano-3-phenoxybenzyl                                                              +12.5                                        32                                                                                    ##STR18##   α-cyano-3-phenoxybenzyl                                                              +12.5                                        33     CH.sub.2 C(CH.sub.3).sub.3                                                                 α-cyano-3-phenoxybenzyl                                                              +17.5                                        34     CH.sub.2 C(CH.sub.3).sub.3                                                                 3-phenoxybenzyl                                                                             +7.5                                        35                                                                                    ##STR19##   3-phenoxybenzyl                                                                             +5.0                                        36     CH.sub.2 CBr(CH.sub.3)CH.sub.2 Br                                                          α-cyano-3-phenoxybenzyl                                                              +11.3                                        37     CH.sub.3     H            +41.7                                        38     CH.sub.2 C.sub.6 H.sub.5                                                                   H            +43.8                                        39     CH(CH.sub.3).sub.2                                                                         H            +45.4                                        40     CH.sub.2 CHCH.sub.2                                                                        H            +42.5                                        41     C.sub.2 H.sub.5                                                                            H                                                         42     C.sub.6 H.sub.5                                                                            H                                                         43     C(CH.sub.3).sub.3                                                                          H            +40.0                                        44     (CH.sub.2).sub.3 CH.sub.3                                                                  H            +32.5                                        45     (CH.sub.2).sub.4 CH.sub.3                                                                  H            +30.6                                        46     (CH.sub.2).sub.5 CH.sub.3                                                                  H            +22.5                                        47     CH.sub.2CH.sub.2CH(CH.sub.3).sub.2                                                         H            +22.5                                        48     CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                                                     H            +18.8                                        49     H            H                                                         50     CH.sub.2 CH(CH.sub.3).sub.2                                                                (CH.sub.2).sub.15 CH.sub.3                                51                                                                                    ##STR20##   H             +2.50                                       52                                                                                    ##STR21##   H            +26.3                                        53                                                                                    ##STR22##   H            +28.0                                        54     CH.sub.2 C(CH.sub.3)CH.sub.2                                                               H            +30.0                                        55     CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                                                     H            +31.2                                        56     CH.sub.2 C(CH.sub.3).sub.3                                                                 H            +12.5                                        57     (CH.sub.2)CHCHCH.sub.3                                                                     H            +25.0                                        58                                                                                    ##STR23##   H            +25.0                                        59     CH.sub.2CHCCl.sub.2                                                                        H            +31.2                                        __________________________________________________________________________

III. Adult female two-spotted spider mites (Tetranychus urticae (Koch))were tested by placing 50-75 mites on the bottom side of leaves of pintobean plants. The leaves were sprayed with dilutions of acetone solutionof test compound into water containing an emulsifier and kept underlaboratory conditions for about 20 hours at which time mortality countswere made. The test were conducted employing several different dosagerates of test compounds.

IV. Mosquito larvae (Anopheles albimanus (Weide)) were tested by placingten living and active mosquito larvae in a jar containing a 0.1 mlaliquot of a 1% acetone solution of test compound thoroughly mixed with100 ml of distilled water. After 18-22 hours, mortality counts weretaken. Both dead and moribund larvae were counted as dead. Larvae whichdid not swim after being prodded with a needle were considered moribund.The tests were conducted employing several different dosage rate foreach test compound.

V. Corn earworm larvae (Heliothis zea (Boddie)) were tested by sprayinga broad bean plant with dilutions of acetone solution of test compoundinto water containing an emulsifier. Immediately after spraying, 5larvae were transferred to the plant and held for 44-46 hours, at whichtime the dead and moribund larvae were counted. The tests were conductedemploying several different dosage rates for each test compound.

In each instance, the toxicity of the compound of the invention wascompared to that of a standard pesticide (Parathion), its relativetoxicity then being expressed in terms of the relationship between theamount of compound of the invention and the amount of the standardpesticide required to produce the same percentage (50) of mortality inthe test insects or acarine. By assigning the standard pesticide inarbitrary rating of 100, the toxicities of the compounds of theinvention were expressed in terms of the toxicity indexes, whichcompares the toxicity of the compounds of the invention with that of thestandard pesticide. That is to say, a test compound having a ToxicityIndex of 50 would be half as active, while one having a Toxicity Indexof 200 would be twice as active as the standard pesticide.

Results of the above tests are shown in Table 3.

It can be seen that the compounds of the invention exhibit toxicityagainst the various pests tested and were particularly effective on cornearworm larvae. Moreover, a number of compounds of the invention areparticularly effective for controlling acarines, such as the two-spottedspider mites as indicated by the compound having a Toxicity Indexagainst mites of about 100 or greater, for example, the compounds ofEmbodiment 18c (the Z-isomer of 3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((isobutoxyimino)methyl)cyclopropanecarboxylate)and Embodiment 23c (the Z-isomer of3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylate).

                  TABLE 4                                                         ______________________________________                                        PESTICIDAL ACTIVITY OF (1R,CIS)CYCLO-                                         PROPANECARBOXYLATE OXIMES EXPRESSED AS                                        TOXICITY INDEX RELATIVE TO THAT OF PARATHION                                  AS A STANDARD EQUAL TO 100                                                             House   Pea     2-Spotted                                                                            Mosquito                                                                             Corn                                   Embodiment                                                                             Fly     Aphid   Mite   Larvae Earworm                                ______________________________________                                         5       100     25      +      17     150                                     6       210     370     26     --     550                                     7       70      120     31     --     230                                     8       57      54      10     --     120                                     9       --      120     8      --     580                                    10       --      140     55     --     670                                     4       81      43      22     --     130                                    12       140     20      5      26     110                                     3       550     6,300   860    400    3,200                                  25b      --      --      --     --     1,700                                  25d      --      --      --     --     2,400                                  11       140     84      5      100    100                                    13       270     250     20     1,400  300                                    16       650     450     55     4,300  390                                     2       760     1,300   80     3,500  1,100                                  14       520     690     34     4,200  920                                    15       110     440     82     500    470                                    22       480     2,500   40     2,200  1,800                                  19       300     440     69     450    330                                    20       440     690     140    3,000  550                                    18a      --      --      --     --     560                                    18b      41      48      40     24     230                                    18c      290     230     310    360    1,300                                  23a      290     100     47     110    440                                    23b      50      33      25     35     310                                    23c      490     200     100    480    790                                    24       70      570     74     390    480                                    26       69      290     81     840    170                                    27       1,400   3,900   400    3,800  1,800                                  28       140     1,000   130    29,000 320                                    29       900     320     49     110    310                                    30       250     880     120    57     900                                    31       120     360     1      150    140                                    32       300     2,300   210    2,200  1,300                                  33       190     360     80     550    820                                    34       44      81      590    33     1,600                                  35       66      160     240    1,100  530                                    36       33      320     38     35     210                                    ______________________________________                                         -- indicates no test.                                                    

Moreover, the (1R,cis) compounds of the invention have been found to beunexpectedly more active in the control of certain pests, particularlythe corn earworm larvae and mites, than the corresponding structurallymost similar (1R,trans) compounds specifically disclosed in U.S. Pat.No. 3,922,269. Examples of such esters of the2,2-dimethyl-3-((oxyimino)methyl)cyclopropanecarboxylic acid arecompared in Tables 5, and 6 below, expressed in terms of Toxicity Indexrelative to parathion as a standard equal to 100.

                                      TABLE 5                                     __________________________________________________________________________    PESTICIDAL ACTIVITY OF α-CYANO-3-PHENOXYBENZYL 3,3-DIMETHYL-3-          ((OXYIMINO)METHYL)CYCLOPROPANECARBOXYLATES EXPRESSED AS TOXICITY              INDEX RELATIVE TO THAT OF PARATHION AS A STANDARD EQUAL TO 100                         Configuration                                                                        E/Z Isomer                                                                           House                                                                             Pea Corn  2-Spotted                                                                          Mosquito                             R'       of Acid                                                                              Content                                                                             Fly Aphid                                                                             Earworm                                                                             Mite Larvae                              __________________________________________________________________________     ##STR24##                                                                             1R,cis.sup.1                                                                         E-Z mixture                                                                          480 2,500                                                                             1,800 40   2,200                               CH.sub.2 CH(CH.sub.3).sub.2                                                            1R,cis.sup.2                                                                         E-Z mixture                                                                          760 1,300                                                                             1,100 80   3,500                               CH.sub.3 1R,cis.sup.3                                                                         E-Z mixture                                                                          100 25  150   +    17                                  CH.sub.3 1R,trans.sup.4                                                                       Z isomer                                                                              35 24  12     0   23                                  CH.sub.3 1R,trans.sup.4                                                                       E isomer                                                                              73 28  27     0   96                                  __________________________________________________________________________     .sup.1 Embodiment 22                                                          .sup.2 Embodiment 2                                                           .sup.3 Embodiment 5                                                           .sup.4 Compound named in Example 5 of U.S. Pat. No. 3,922,269.                + Toxicity Index means >0 but <1.                                        

                                      TABLE 6                                     __________________________________________________________________________    PESTICIDAL ACTIVITY OF 3-PHENOXYBENZYL 3,3-DIMETHYL-3-((OXYIMINO)-            METHYL)CYCLOPROPANECARBOXYLATES EXPRESSED AS TOXICITY INDEX                   RELATIVE TO THAT OF PARATHION AS A STANDARD EQUAL TO 100                               Configuration                                                                        E/Z Isomer                                                                            House                                                                             Pea Corn  2-Spotted                                                                          Mosquito                            R.sup.1  of Acid                                                                              Content                                                                              Fly Aphid                                                                             Earworm                                                                             Mite Larvae                             __________________________________________________________________________     ##STR25##                                                                             1R,cis.sup.1                                                                         Z isomer                                                                             490  200 790   100  480                                CH.sub.2 CH(CH.sub.3).sub.2                                                            1R,cis.sup.2                                                                         Z isomer                                                                             290  230 1,300 310  360                                CH.sub.3 1R,cis.sup.3                                                                         E-Z mixture                                                                          140  20  110   5    26                                 CH.sub.3 1R,trans.sup.4                                                                       80% E isomer/                                                                         78  3.8 23    0    5.4                                                20% Z isomer                                                  CH.sub.3 1R,trans.sup.4                                                                       85% Z isomer/                                                                         66  3.2 28    0    4.2                                                15% E isomer                                                  __________________________________________________________________________     .sup.1 Embodiment 23c                                                         .sup.2 Embodiment 18c                                                         .sup.3 Embodiment 12                                                          .sup.4 Compound named in Examples 6 of U.S. Pat. No. 3,922,269                 + Toxicity Index means >0 but <1.                                       

We claim:
 1. A (1R,cis)-cyclopropane compound, substantially free ofother stereoisomers, having the formula ##STR26## wherein R¹ is a(cycloalkyl)alkyl group containing 3 to 6 ring carbon atoms and 4 to 8total carbon atoms and X is chlorine, bromine or OR in which Rrepresents a hydrogen atom, a salt-forming cation, an alkyl groupcontaining from 1 to 20 carbon atoms, 3-phenoxybenzyl orα-cyano-3-phenoxybenzyl, with the proviso that when R isα-cyano-3-phenoxybenzyl then the alcohol moiety is in the R,S-racemic orin the S-optical configuration.
 2. A compound according to claim 1wherein R¹ is a (cycloalkyl)alkyl group containing from 4 to 5 carbonatoms and X is OR in which R is α-cyano-3-phenoxybenzyl or3-phenoxybenzyl.
 3. A compound according to claim 2 wherein R isα-cyano-3-phenoxybenzyl.
 4. A compound according to claim 2 wherein R is3-phenoxybenzyl.
 5. A compound according to claims 2, 3 or 4, inclusive,wherein the oxime substituent is substantially in the Z isomer form. 6.An insecticidal or acaricidal composition comprising an insecticidallyor acaricidally effective amount of an oxyimino-substituted(1R,cis)cyclopropane compound according to claim 2 and at least oneagriculturally acceptable surface-active agent or carrier therefore. 7.A method of controlling insect or acarine pests at a locus whichcomprises applying to the insect or acarine pests or to the locus apesticidally effective amount of an oxyimino-substituted(1R,cis)cyclopropane compound according to claim
 2. 8. A methodaccording to claim 7 wherein the pests are selected from the order ofColeoptera, Lepidoptera, Diptera, Orthoptera, Hemiptera, Homoptera orAcarina.
 9. A method according to claim 8 wherein in the pests arelarvae of the order Lepidoptera.
 10. A method according to claim 8wherein the pests are of the order Acarina.
 11. α-Cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylate,in which the alcohol moiety is in the R,S-racemic or S-opticalconfiguration, substantially free of other stereoisomers. 12.α-Cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((cyclobutylmethoxyimino)methyl)cyclopropanecarboxylate,in which the alcohol moiety is in the R,S-racemic or S-opticalconfiguration, substantially free of other stereoisomers. 13.3-Phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((cyclobutylmethoxyimino)methyl)cyclopropanecarboxylate,substantially free of other stereoisomers.
 14. 3-Phenoxybenzyl(1R,cis)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylate,substantially free of other stereoisomers.